CN107686577B - Polyethylene composition, application, laser sintering method and three-dimensional product - Google Patents
Polyethylene composition, application, laser sintering method and three-dimensional product Download PDFInfo
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- CN107686577B CN107686577B CN201610631177.0A CN201610631177A CN107686577B CN 107686577 B CN107686577 B CN 107686577B CN 201610631177 A CN201610631177 A CN 201610631177A CN 107686577 B CN107686577 B CN 107686577B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
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Abstract
The invention relates to the field of selective laser sintering, and discloses a polyethylene composition, application thereof, a laser sintering method and a three-dimensional product. Wherein the polyethylene composition contains granular ultrahigh molecular weight polyethylene and granular inorganic filler, the viscosity average molecular weight of the ultrahigh molecular weight polyethylene is 150-500 ten thousand, and the particle size of the ultrahigh molecular weight polyethylene is 20-200 mu m; the particle size of the inorganic filler is 2.6-25 μm. The three-dimensional product prepared by selective laser sintering of the polyethylene composition provided by the invention has the advantages of smooth surface, hard texture and strong wear resistance.
Description
Technical Field
The invention relates to the field of selective laser sintering, in particular to a polyethylene composition and application thereof, a laser sintering method and a three-dimensional product.
Background
Selective Laser Sintering (SLS) is one of the currently widely used rapid prototyping technologies, which uses solid powder as a raw material, and directly manufactures a three-dimensional entity from a CAD model by adopting a layering-stacking principle, theoretically, any powder with reduced viscosity during heating can be used as an SLS Sintering material, and the wide material obtaining range is one of the important factors that the SLS process can be widely applied to various fields. Repeated irradiation of the newly applied layers in a constant sequence by this method allows for simple and rapid manufacture of three-dimensional products.
In addition, the SLS product can obtain a molded part with high strength and good toughness without injection molding, can be directly used for testing the strength and performance of a model, verifies the reasonability of a product design structure, the feasibility of a manufacturing process and the attractiveness of the shape, and can modify and perfect the product design in time so as to meet the market requirement, thereby greatly shortening the development period of a new product, reducing the development cost and enabling an enterprise to have stronger competitive power.
Laser sintering processes for preparing moldings from pulverulent polymers are described in detail in issued patents 200410030462.4 and 200480032696.0. Polymers may be used in SLS, but it is noted that a material for SLS processing is premised on the material being a fine powder.
In practice, specific materials which are frequently used for the preparation of moldings by the laser sintering process are nylon-12 powder (PA-12) and polystyrene Powder (PS). Both materials present some problems in practical applications. For example, nylon-12 powder and polystyrene powder have low strength and rigidity, and products formed by SLS techniques do not satisfy the mechanical property test requirements of some formed parts or the property requirements for direct use as end products.
Disclosure of Invention
The invention provides a novel polyethylene composition and application thereof, and a selective laser sintering method and a three-dimensional product.
Ultra-high molecular weight polyethylene has many advantages, such as excellent toughness and wear resistance. There is no report of the use of ultra high molecular weight polyethylene for selective laser sintering processes. This may be due to too high a molecular weight resulting in too high a viscosity that is detrimental to the dusting in the selective laser sintering process. In addition, the defects of the ultra-high molecular weight polyethylene powder used in other fields, such as the insufficient uniformity of the shape and the particle size distribution, and the poor heat resistance of the powder, also limit the use of the ultra-high molecular weight polyethylene powder as a raw material for a laser sintering process. The existing ultra-high molecular weight polyethylene powder material has strict requirements on sintering processes, and different sintering processes can influence the quality of SLS three-dimensional products. However, after intensive research, the inventors of the present invention found that when ultra-high molecular weight polyethylene having a viscosity average molecular weight of 150 to 500 ten thousand and a particle size of 20 to 200 μm is used in combination with an inorganic filler having a particle size of 2.6 to 25 μm, the resulting polyethylene composition has excellent flowability, heat resistance and wear resistance, and a three-dimensional product having a smooth surface, a hard texture and high wear resistance can be prepared by selective laser sintering. The present inventors have completed the present invention based on the above findings.
Specifically, in a first aspect, the present invention provides a polyethylene composition comprising a granular ultra-high molecular weight polyethylene having a viscosity average molecular weight of 150 to 500 ten thousand and a granular inorganic filler, the ultra-high molecular weight polyethylene having a particle size of 20 to 200 μm; the particle size of the inorganic filler is 2.6-25 μm.
In a second aspect, the invention also provides the use of a polyethylene composition as described above in selective laser sintering.
In a third aspect, the present invention also provides a selective laser sintering method, which includes selectively sintering a powder material by using a laser, wherein the powder material is the polyethylene composition.
In a fourth aspect, the invention also provides a three-dimensional article obtained by the above method.
The polyethylene composition provided by the invention has the advantages of good fluidity, heat resistance, abrasion resistance, uniform particle size distribution and the like. The composition is applied to a selective laser sintering process, and a three-dimensional product with a smooth surface, a hard surface and high wear resistance can be obtained. In particular, the polyethylene compositions according to the present invention can be used to produce three-dimensional articles by selective laser sintering, whereas the polyethylene compositions not according to the present invention do not provide complete three-dimensional articles or give three-dimensional articles with a very rough surface. The three-dimensional product prepared by the invention has the advantages of good appearance, smooth surface, high tensile strength, large tensile strain at break, small abrasion, high load deformation temperature and excellent performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a three-dimensional article B1 prepared in example 1;
fig. 2 is a three-dimensional article B2 prepared in example 2.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a polyethylene composition, wherein the polyethylene composition contains granular ultra-high molecular weight polyethylene and granular inorganic filler, the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150-500 ten thousand, and the grain diameter of the ultra-high molecular weight polyethylene is 20-200 mu m; the particle size of the inorganic filler is 2.6-25 μm.
In the present invention, the weight ratio of the ultra-high molecular weight polyethylene and the inorganic filler may vary within a wide range. For example, the weight ratio of the ultra-high molecular weight polyethylene to the inorganic filler may be 4 to 99: 1. In order to obtain a composition having better properties, for example, in order to obtain a composition having better flowability, heat resistance, abrasion resistance, etc., the weight ratio of the ultrahigh-molecular weight polyethylene to the inorganic filler is preferably 7 to 32:1, more preferably 9 to 19: 1.
According to the invention, the said ultra-high molecular weight polyethylene is understood by those skilled in the art and its density is generally between 0.93 and 0.96g/cm3The heat distortion temperature is generally from 85 to 90 ℃. The viscosity average molecular weight of the ultra-high molecular weight polyethylene in the invention is 150 to 500 ten thousand, preferably 200 to 450 ten thousand, and more preferably 300 to 400 ten thousand.
In the present invention, the particle size of the ultra-high molecular weight polyethylene is preferably 30 to 150 μm, more preferably 40 to 100 μm, in order to obtain a composition having better properties, although it is satisfactory as long as it satisfies the above-mentioned 20 to 200 μm.
In the present invention, the ultra-high molecular weight polyethylene may be prepared by various methods in the related art, or may be commercially available, as long as the viscosity average molecular weight and the particle diameter thereof satisfy the requirements. The method for obtaining polyethylene meeting the particle size requirement from the ultra-high molecular weight polyethylene is not particularly limited, and various conventional means in the field can be adopted. The invention preferably adopts a winnowing mode to select the ultra-high molecular weight polyethylene meeting the requirement of the particle size. The process of air classification, including equipment and conditions, may be selected as is conventional in the art. For example, the winnowing process comprises: the powder falls on a high-speed rotating distribution disc through a winnowing machine and a feed hopper under the action of wind power transmission, the materials are fully dispersed and thrown to a buffer ring under the action of centrifugal force, and in the falling process, the heavier materials slide into a coarse material collector of a separator through blades of an adjusting ring under the action of cross airflow generated by a rotor and are collected, and then the materials are discharged through a fan; and the lighter materials are conveyed to a micro powder collector of a classifier below along with the air flow of an air suction port in the middle part above the rotor under the action of cross air flow to be collected, and then are discharged by a fan.
In the present invention, the particle size of the inorganic filler may vary within a wide range. According to a preferred embodiment of the invention, the particle size of the inorganic filler is 6.5 to 23 μm, more preferably 6.5 to 18 μm. The particle size of the inorganic filler may also be in "mesh" units. For example, the particle size of the inorganic filler is 2.6-25 μm, and the corresponding particle size is 500-5000 mesh. The particle size of the inorganic filler is preferably 600-2000 mesh, and more preferably 800-2000 mesh.
In the present invention, the particle size of the inorganic filler may be controlled by means of sieving. The manner of sieving is well known to those skilled in the art. For example, the inorganic filler with the particle size of 500-5000 meshes can be obtained by sieving the inorganic filler with a 500-mesh sieve, sieving the sieved substance with a 5000-mesh sieve, and the inorganic filler left on the 5000-mesh sieve is the inorganic filler meeting the particle size requirement.
In the present invention, the kind of the inorganic filler is not particularly limited, and may be conventionally selected in the art, and may be, for example, one or more of silica, glass beads, talc, barium sulfate, montmorillonite and silica micropowder. Preferably, the inorganic filler is one or more of silica, glass beads and silica micropowder.
According to a preferred embodiment of the present invention, the composition may further comprise an antioxidant. The type of antioxidant may be a matter of routine choice in the art. For example, the antioxidant may be a hindered phenol antioxidant and/or a phosphite antioxidant; preferably, the antioxidant is one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (also called antioxidant 1010), tris [2, 4-di-tert-butylphenyl ] phosphite (also called antioxidant 168) and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (also called antioxidant 1076); the antioxidant may also be a built antioxidant, such as antioxidant B215 (antioxidant 1010: antioxidant 168 ═ 1: 2 by weight) and/or antioxidant B225 (antioxidant 1010: antioxidant 168 ═ 1: 1 by weight). More preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant B215 and antioxidant B225.
In the present invention, the amount of the antioxidant may be conventionally selected in the art. For example, the antioxidant may be present in the polyethylene composition in an amount of 0.2 to 0.5 wt%, preferably 0.25 to 0.35 wt%, based on the total weight of the polyethylene composition.
The present invention does not particularly limit the preparation method of the polyethylene composition, as long as all the components can be uniformly mixed. According to a preferred embodiment, the process for producing the polyethylene composition comprises the steps of: and (2) uniformly mixing the ultra-high molecular weight polyethylene with the particle size of 20-200 mu m and the inorganic filler with the particle size of 2.6-25 mu m by using a high-speed stirrer to obtain the polyethylene composition, wherein the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150-500 ten thousand. According to a more preferred embodiment, the components to be mixed also contain the antioxidant, in which case the antioxidant is used in an amount such that it is present in an amount of 0.2 to 0.5% by weight, based on the total weight of the composition.
The invention also provides the use of the above polyethylene composition in selective laser sintering.
The invention also provides a selective laser sintering method, which comprises the step of selectively sintering the powder material by using laser, wherein the powder material is the polyethylene composition.
The method of selective laser sintering provided by the present invention preferably further comprises preheating the powder material to 128-132 ℃ before performing selective sintering.
The main improvement of the selective laser sintering method provided by the invention is that a new sintering raw material is provided, and the specific process of the selective laser sintering can be the same as that of the existing method. For example, according to one embodiment of the present invention, the method of selective laser sintering comprises: when the forming starts, the forming cylinder workbench is lowered by one layer thickness, powder materials with one layer thickness are laid, the powder materials in the layer are preheated, the temperature of the powder materials is slightly lower than the melting point of the powder materials, then, laser beams are used for selectively sintering the powder materials under the control of a computer according to the profile information of a model in the computer, after one layer is finished, the plane of the layer is obtained, the workbench is lowered by one layer height, a layer of powder materials is laid, the sintering is continuously repeated, and finally the three-dimensional product is obtained. The powdered material in this process is the polyethylene composition described above.
In the present invention, the thickness of the sintered layer is 0.15 to 0.25 mm. The "thickness of the sintered layer" refers to the thickness of the sintered layer obtained by each laser sintering.
The conditions for the selective laser sintering are not particularly limited in the present invention, and for example, generally include: the laser power output ratio may be 30-70% and the scanning speed may be 0.5-2 m/s.
The invention also provides a three-dimensional product prepared by the method. The three-dimensional product has smooth surface, hard quality and strong wear resistance.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples,
ultra-high molecular weight polyethylene was purchased from Yanshan petrochemical;
inorganic filler silica was purchased from a new Qingdao Newson gram material with a brand number VN 3;
the inorganic filler glass beads are purchased from Shanghai brand glass New materials Co., Ltd and are under the brand number MH;
the inorganic filler barium sulfate is purchased from Shanghai Liangjiang titanium white chemical products, Inc.;
the inorganic filler silicon powder is purchased from Hongrun quartz silicon powder company Limited;
antioxidants were purchased from Shijiazhuang Jiatuo chemical technology Co., Ltd under the designations 1010 and 168.
The laser sintering equipment is purchased from Beijing Longyuan automatic molding systems, Inc., and has the brand number of AFS-360.
The test method of tensile strength and tensile strain at break is GB/T1040.2-2006, and according to the size requirement of the test method, the polyethylene composition in the embodiment is used for selective laser sintering sample preparation, and then the test is carried out.
The abrasion performance test method is ISO 15527: 2010, the deformation temperature under load test method is GB/T1634.2-2004.
Example 1
This example illustrates the polyethylene composition provided by the instant invention, its method of preparation and use.
(1) Preparation of polyethylene compositions
The ultra-high molecular weight polyethylene with the viscosity average molecular weight of 350 ten thousand is winnowed, and the grain diameter of the ultra-high molecular weight polyethylene is controlled to be 40-100 mu m. Sieving the silicon dioxide, and controlling the particle size of the silicon dioxide to be 6.5-18 mu m. 9000 g of wind-selected ultrahigh molecular weight polyethylene, 1000 g of sieved silica, 10 g of antioxidant 1010 and 20 g of antioxidant 168 were mixed uniformly by a high-speed mixer to prepare a polyethylene composition A1.
(2) Selective laser sintering
The polyethylene composition A1 is used as a raw material to carry out selective laser sintering. When the forming starts, the working table of the forming cylinder is lowered by one layer thickness, powder with one layer thickness is laid, the powder with the layer thickness is preheated, the temperature of the powder is slightly lower than the melting point of the powder, then, the laser beam selectively sinters the powder material under the control of a computer according to the outline information of a model in the computer, after one layer is finished, the plane of the layer is obtained, the working table is lowered by one layer height again, then, the powder with one layer thickness is laid, the sintering is continuously repeated, and finally, the three-dimensional product is obtained. The technological parameters are as follows: the laser power output ratio was 50%, the scanning speed was 1.5m/s, the thickness of the sintered layer was 0.2mm, and the preheating temperature was 130 ℃. A three-dimensional article B1 was prepared. Fig. 1 is a picture of the three-dimensional product B1, and the reference object in fig. 1 is a latest version of the 1-horn coin. As can be seen from fig. 1, the three-dimensional article B1 has a smooth surface. The results of the performance tests of the three-dimensional article B1 are listed in table 1.
Example 2
This example illustrates the polyethylene composition provided by the instant invention, its method of preparation and use.
(1) Preparation of polyethylene compositions
The ultra-high molecular weight polyethylene with the viscosity-average molecular weight of 300 ten thousand is winnowed, and the grain diameter of the ultra-high molecular weight polyethylene is controlled to be 40-100 mu m. And screening the glass beads, wherein the particle size of the glass beads is controlled to be 6.5-18 mu m. And uniformly mixing 9300 g of wind-screened ultrahigh molecular weight polyethylene, 700 g of sieved glass microspheres, 15 g of antioxidant 1010 and 10 g of antioxidant 168 by using a high-speed stirrer to prepare a polyethylene composition A2.
(2) Selective laser sintering
The polyethylene composition A2 is used as a raw material to carry out selective laser sintering. When the forming starts, the working table of the forming cylinder is lowered by one layer thickness, powder with one layer thickness is laid, the powder with the layer thickness is preheated, the temperature of the powder is slightly lower than the melting point of the powder, then, the laser beam selectively sinters the powder material under the control of a computer according to the outline information of a model in the computer, after one layer is finished, the plane of the layer is obtained, the working table is lowered by one layer height again, then, the powder with one layer thickness is laid, the sintering is continuously repeated, and finally, the three-dimensional product is obtained. The technological parameters are as follows: the laser power output ratio was 30%, the scanning speed was 0.5m/s, the thickness of the sintered layer was 0.15mm, and the preheating temperature was 128 ℃. A three-dimensional article B2 was prepared. Fig. 2 is a picture of the three-dimensional product B2, and the reference object in fig. 2 is a latest version of the 1-horn coin. As can be seen from fig. 2, the three-dimensional article B2 has a smooth surface. The results of the performance tests of the three-dimensional article B2 are listed in table 1.
Example 3
This example illustrates the polyethylene composition provided by the instant invention, its method of preparation and use.
(1) Preparation of polyethylene compositions
The ultra-high molecular weight polyethylene with the viscosity average molecular weight of 400 ten thousand is winnowed, and the grain diameter of the ultra-high molecular weight polyethylene is controlled to be 40-100 mu m. Sieving the silicon powder, and controlling the particle size of the silicon powder to be 6.5-18 mu m. And uniformly mixing 9500 g of wind-screened ultrahigh molecular weight polyethylene, 500 g of sieved silica powder, 17.5 g of antioxidant 1010 and 17.5 g of antioxidant 168 by using a high-speed stirrer to prepare the polyethylene composition A3.
(2) Selective laser sintering
The polyethylene composition A3 is used as a raw material to carry out selective laser sintering. When the forming starts, the working table of the forming cylinder is lowered by one layer thickness, powder with one layer thickness is laid, the powder with the layer thickness is preheated, the temperature of the powder is slightly lower than the melting point of the powder, then, the laser beam selectively sinters the powder material under the control of a computer according to the outline information of a model in the computer, after one layer is finished, the plane of the layer is obtained, the working table is lowered by one layer height again, then, the powder with one layer thickness is laid, the sintering is continuously repeated, and finally, the three-dimensional product is obtained. The technological parameters are as follows: the laser power output ratio was 70%, the scanning speed was 2m/s, the thickness of the sintered layer was 0.25mm, and the preheating temperature was 132 ℃. A three-dimensional article B3 was prepared. The three-dimensional article B3 had a smooth surface. The results of the performance tests of the three-dimensional article B3 are listed in table 1.
Example 4
This example illustrates the polyethylene composition provided by the instant invention, its method of preparation and use.
(1) Preparation of polyethylene compositions
A polyethylene composition was prepared according to the method of example 1, except that the particle size of the ultra-high molecular weight polyethylene was controlled to 30 to 150. mu.m. Polyethylene composition a4 was prepared.
(2) Selective laser sintering
Selective laser sintering was carried out in accordance with the procedure of example 1, except that a polyethylene composition A4 was used as the starting material in place of A1. A three-dimensional article B4 was prepared. The three-dimensional article B4 was able to be molded, but the smoothness of the surface was slightly inferior to that of B1. The results of the performance tests of the three-dimensional article B4 are listed in table 1.
Example 5
This example illustrates the polyethylene composition provided by the instant invention, its method of preparation and use.
(1) Preparation of polyethylene compositions
A polyethylene composition was prepared according to the method of example 1, except that the particle size of the ultra-silica was controlled to 6.5 to 23 μm. Polyethylene composition a5 was prepared.
(2) Selective laser sintering
Selective laser sintering was carried out in accordance with the procedure of example 1, except that a polyethylene composition A5 was used as the starting material in place of A1. A three-dimensional article B5 was prepared. The three-dimensional article B5 was able to be molded, but the smoothness of the surface was slightly inferior to that of B1. The results of the performance tests of the three-dimensional article B5 are listed in table 1.
Example 6
This example illustrates the polyethylene composition provided by the instant invention, its method of preparation and use.
(1) Preparation of polyethylene compositions
A polyethylene composition was prepared according to the method of example 1, except that the weight ratio of the ultra-high molecular weight polyethylene to the inorganic filler, silica, was 30: 1, producing a polyethylene composition a 6.
(2) Selective laser sintering
Selective laser sintering was carried out in accordance with the procedure of example 1, except that a polyethylene composition A6 was used as the starting material in place of A1. A three-dimensional article B6 was prepared. The results of the performance tests of the three-dimensional article B6 are listed in table 1.
Example 7
This example illustrates the polyethylene composition provided by the instant invention, its method of preparation and use.
(1) Preparation of polyethylene compositions
A polyethylene composition was prepared according to the method of example 1, except that the weight ratio of the ultra-high molecular weight polyethylene to the inorganic filler, silica, was 3: 1, producing a polyethylene composition a 7.
(2) Selective laser sintering
Selective laser sintering was carried out in accordance with the procedure of example 1, except that a polyethylene composition A7 was used as the starting material in place of A1. A three-dimensional article B7 was prepared. The three-dimensional article B7 was substantially formable, but had a partial region that was not completely melted, and had a slightly less precise and rough surface.
Example 8
This example illustrates the polyethylene composition provided by the instant invention, its method of preparation and use.
(1) Preparation of polyethylene compositions
A polyethylene composition was prepared according to the method of example 1.
(2) Selective laser sintering
Selective laser sintering was carried out in the same manner as in example 1 except that the laser output ratio in the sintering process was 20%, to prepare a three-dimensional article B8. The three-dimensional article B8 could be shaped but some areas were not completely melted.
Comparative example 1
This comparative example serves to illustrate a reference polyethylene composition, a process for its preparation and its use.
(1) Preparation of polyethylene compositions
A polyethylene composition was prepared according to the method of example 1, except that the polyethylene composition did not contain the inorganic filler, silica. The polyethylene composition DA1 was prepared.
(2) Selective laser sintering
Selective laser sintering was carried out in accordance with the procedure of example 1, except that a polyethylene composition DA1 was used as the starting material in place of A1. As a result, a complete three-dimensional article cannot be obtained.
Comparative example 2
This comparative example serves to illustrate a reference polyethylene composition, a process for its preparation and its use.
(1) Preparation of polyethylene compositions
A polyethylene composition was prepared according to the method of example 1, except that the particle size of the silica was controlled to be greater than 25 μm. The polyethylene composition DA2 was prepared.
(2) Selective laser sintering
Selective laser sintering was carried out in accordance with the procedure of example 1, except that a polyethylene composition DA2 was used as the starting material in place of A1. A three-dimensional product DB3 was prepared. The three-dimensional product DB3 has a very rough surface.
Comparative example 3
This comparative example serves to illustrate a reference polyethylene composition, a process for its preparation and its use.
(1) Preparation of polyethylene compositions
A polyethylene composition was prepared according to the method of example 1, except that the particle size of the ultra-high molecular weight polyethylene was controlled to be more than 200. mu.m. The polyethylene composition DA3 was prepared.
(2) Selective laser sintering
Selective laser sintering was carried out in accordance with the procedure of example 1, except that a polyethylene composition DA3 was used as the starting material in place of A1. As a result, a complete three-dimensional article cannot be obtained.
Comparative example 4
This comparative example serves to illustrate a reference polyethylene composition, a process for its preparation and its use.
(1) Preparation of polyethylene compositions
A polyethylene composition was prepared according to the method of example 1, except that the particle size of the ultra-high molecular weight polyethylene was controlled to be less than 20 μm. The polyethylene composition DA4 was prepared.
(2) Selective laser sintering
Selective laser sintering was carried out in accordance with the procedure of example 1, except that a polyethylene composition DA4 was used as the starting material in place of A1. Because the ultrahigh particle size is too fine, the adhesion is serious, and the powder can not be spread basically in the sintering process.
Comparative example 5
This comparative example serves to illustrate a reference polyethylene composition, a process for its preparation and its use.
(1) Preparation of polyethylene compositions
A polyethylene composition was prepared according to the method of example 1, except that the inorganic filler, silica, was controlled to be less than 2.6 μm. The polyethylene composition DA5 was prepared.
(2) Selective laser sintering
Selective laser sintering was carried out in accordance with the procedure of example 1, except that a polyethylene composition DA5 was used as the starting material in place of A1. The inorganic substance has too fine particle size and serious agglomeration, and a complete three-dimensional product can not be obtained basically.
TABLE 1
As can be seen from the results of the examples and the comparative examples, the polyethylene composition provided by the invention adopts the selective laser sintering to obtain a three-dimensional product with smooth surface, hard quality and strong wear resistance. In particular, examples 1 to 8 all produced three-dimensional articles, and comparative examples 1 to 5, which did not use the polyethylene composition of the present invention, did not produce complete three-dimensional articles or produced three-dimensional articles having a very rough surface. The three-dimensional products prepared by the most preferred embodiment of examples 1-3 have good appearance, smooth surface, high tensile strength, large tensile strain at break, low abrasion and high load deformation temperature, which shows that the three-dimensional products of examples 1-3 have excellent performance.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (18)
1. The polyethylene composition is characterized by comprising granular ultrahigh molecular weight polyethylene and granular inorganic filler, wherein the viscosity average molecular weight of the ultrahigh molecular weight polyethylene is 150-500 ten thousand, and the particle size of the ultrahigh molecular weight polyethylene is 30-150 mu m; the particle size of the inorganic filler is 2.6-25 μm;
wherein, in the polyethylene composition, the weight ratio of the ultra-high molecular weight polyethylene to the inorganic filler is 4-99: 1.
2. The polyethylene composition according to claim 1, wherein the weight ratio of the ultra high molecular weight polyethylene and the inorganic filler in the polyethylene composition is 7-32: 1.
3. The polyethylene composition according to claim 2, wherein the weight ratio of the ultra high molecular weight polyethylene and the inorganic filler is 9-19: 1.
4. The polyethylene composition of claim 1, wherein the ultra high molecular weight polyethylene has a viscosity average molecular weight of from 200 to 450 ten thousand.
5. The polyethylene composition according to claim 4, wherein the ultra high molecular weight polyethylene has a viscosity average molecular weight of from 300 to 400 ten thousand.
6. The polyethylene composition according to claim 1, wherein the ultra high molecular weight polyethylene has a particle size of 40-100 μm.
7. The polyethylene composition according to claim 1, wherein the particle size of the inorganic filler is 6.5-23 μm.
8. The polyethylene composition according to claim 7, wherein the particle size of the inorganic filler is 6.5-18 μm.
9. The polyethylene composition according to claim 1, wherein the inorganic filler is one or more of silica, glass microspheres, talc, barium sulfate, montmorillonite and silica micropowder.
10. The polyethylene composition according to claim 1, wherein the polyethylene composition further comprises an antioxidant.
11. The polyethylene composition according to claim 10, wherein the antioxidant is a hindered phenolic antioxidant and/or a phosphite antioxidant.
12. The polyethylene composition according to claim 11, wherein the antioxidant is one or more of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite, n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
13. The polyethylene composition according to claim 12, wherein the antioxidant is present in the polyethylene composition in an amount of from 0.2 to 0.5 wt%, based on the total weight of the polyethylene composition.
14. Use of a polyethylene composition according to any of claims 1 to 13 in selective laser sintering.
15. A process for selective laser sintering, comprising selective sintering of a powdered material by means of a laser, characterized in that the powdered material is a polyethylene composition according to any of claims 1-13.
16. The method as claimed in claim 15, further comprising preheating the powder material to 128-132 ℃ prior to the selective sintering.
17. The method of claim 15, wherein the sintered layer has a thickness of 0.15-0.25 mm; the selective sintering conditions include a laser power output ratio of 30-70% and a scanning speed of 0.5-2 m/s.
18. A three-dimensional article obtained by the method of any one of claims 15-17.
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| CN103980395A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Ultrahigh-molecular-weight atactic polypropylene resin capable of being used for 3D printing, and preparation method and application thereof |
| CN103980608A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Polypropylene nanocomposite material capable of being used for 3D printing, and preparation method and application thereof |
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| WO2015199244A1 (en) * | 2014-06-27 | 2015-12-30 | 株式会社フジミインコーポレーテッド | Formation material and formation method which are used for forming structure |
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| WO2015199244A1 (en) * | 2014-06-27 | 2015-12-30 | 株式会社フジミインコーポレーテッド | Formation material and formation method which are used for forming structure |
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